Colored photographic pictures



\ Patented Oct. 24, 1939 COLORED PHOTOGRAPHIC PICTURES Lothar Jakob and Bruno Wendt, Dessan, Germany, assignors, by mesne assignments, to

Agfa Ansco Corporation, corporation of Delaware Binghamton, N. Y., a

No Drawing. Application March 24, 1938, semi No. 197,866. In Germany April 9,- 1937 Claims.

Our present invention relates to the productionof photographic color pictures.

The production of azo-dyestufis in light-sensi tive' layers by treating silver halide pictures ob- -5 tained by the reversal process or by bleaching out the silver image with diazonium compounds described in U. S. Patent No. 1,968,956, dated August 7, 1934 or with antidiazotates disclosed in U. S. Patent 'No. 1,963,197, dated June 19, 1934,

is known. It is also known to form dyestuffs-by development at the places of silver of the image by means of azo-dyestuff components which are insoluble in water (see U. S. Patent No. 1,758,572, dated May 13, 1930).

It is one object of our invention to provide an improved process of producing azo-dyestufi' pictures. I

Another object is the provision of a process for the production of such pictures which has the advantage that difiusion oi the dyestufi component is greatly reduced, whereby the sharpness of the picture and also, in the case of multi-layer 7 material, the color rendering, is particularly good.

Further objects of. the invention will appear,

from the following disclosure.

According to the invention the diazotizable dyestufi component of a layer is transformed with the silver halide of the pictureinto a silver compound having a' solubility as low asvthat of the silver halide. l The diazotization and the coupling in the layer then follow, during which the original combination with the silver, and therewith the low solubility of the compound, remains intact.

Compounds which may be used in the invention are, for example, those which contain the group SH (mercapto) -CECH (ethinyl) or =NH (imino) in so far as the H-atom can be exchanged for a metal. .Some of these will be mentioned by way of example:

4!) i\3-aminophenyl-methyl-ethinyl-carbinol,3eamino 7 4 7 methoxyphenyl methyl ethinylcarbinol, para aminophenyl ethinylmethane, 2v-aminonaphthyl-methyl-ethinyl carbinol, para-aminophenylacetylene, the jan'tidiazotate irom bis- (para-aminophenyl-l ethinyl-carbinol'. and C- aminotriazole; meta-aminothiophenol, G-amino;

Z-mercapto-benzthiazole,

Cyanuric chloride can, for example, be caused to react withdiamines, nitro-amines or nitrophenols, whereby after substituting an SH-group for at least one chlorine atom and if necessary after reduction of theintro-group diazotizable mercapto-compounds, which, after coupling, give colors in all desired shades, are obtained. Such compounds are, for example: Z-para-aminophen;

yl-amino-4.6-dimercapto-1.3.5-triazole,- 2-paraaminophenylhydroxy-4.6-dimercapto -.1.3.5 triazole, '2.4+bis-para-aminophenylamino-G-mercapto-1.3.5-triazole,' 2.5'-aminonaphthylamino 4 para-sulfophenylamine-fi-mercapto-1.3.5-triazole. These amines can, if desired, be caused to react in the form of their salts in alkaline solutionwith the silver halide of the picture, diazotized after washing and coupled with a component subsequently introduced into, or originally present in, the layer. The silver halide can then be removed by fixing or in any other known manner. Y Instead of the amines there may be used their antidiazotates. In comparison with the process disclosed in U. S. Patent 'No. 1,963,197 one obtains by the invention the advantage that an extended range of dyestuffs can be used, since one can now use a number of antidiazotates of which the silver antidiazotates are too easily soluble for the reaction with silver halides.

The invention is well suited for the production of multi-color pictures in multi-layer material.

The invention is illustrated by the following examples but they are not intended to limit'it thereto.

1. A silver bromide picture is bathed for 5 minutes in a solution of 1 per cent. strength of 6-amino-2-mercapto-\benzthiazole made weakly alkaline by caustic soda and containing 1 per cent. of sodium sulfite, washed with water containing sulfite for 15 minutes, diazotized in an acidified nitrite solution and, after washing out the, nitrite, coupled with a solution of p-naphthol in caustic soda to give a brown-red dyestufi.

2. A silver halide picture of which the emulsion is cast with an addition of erucayl-K-acid corresponding with the following formula OH 1311.00.(GHz)n.CH=OH.(CH:)1.CH:

is bathed for 10 minutes in the following solution:

After thorough washing, the picture is diazotized in a solutioncontaining 300 cc. of water, 3 grams of sodium nitrite, 20 cc. of acetic acid of 10 per cent. strength and 2 grams of sodium acetate. After allowing penetration for 3-6 minutes and washing for a short time, the erucayl-K-acid present in the layer is coupled in dilute ammonia to give a purple picture.

3. A silver halide picture in a layer containing an azo-dyestuff 'coupling component fast to 'diffusion, for example the pyrazolone produced by condensing a-hydrazino-stearic acid with acetoacetic ester, is treated for 10 minutes with 300 cc. of an aqueous solution of 3 grams oforthoaminophenyl-phenyl-ethinylcarbinol antidiazotate containing 4 cc. of caustic soda lye of per cent. strength. After washing, the pyrazolone is converted into the diafionium compoundin a bath containing 1000 cc. of water, 10 grams of citric acid and 10 grams of common salt, coupled to form the dyestuff and fixed in a normal fixing bath. The picture is yellow.

We claim: I

l. A process of producing colored photographic pictures which comprises exposing to light a photographic material provided with at least one emulsion layer containing a light-sensitive silver halide, transforming the latent image into a silver halide image, converting said silver halide image by a compound selected from the group consisting of an amine capable of being diazotized and an antidiazotate thereof, said compound containing a molecular grouping selected from the group consisting of mercapto-group, ethinylgroup and imino-group, the hydrogen atom of said molecular grouping being capable of being exchanged for a metal, into an image of the corresponding organic silver compound and transforming said image into an azo-dyestufi picture.

2. A process of producing colored photographic pictures which comprises exposing to light a' photographic material provided with at least one emulsion layer containing a light-sensitive silver halide, transforming the latent image into a silver halide image, converting said silver halide image by a compound selected from the group consisting of an amine capable of being diazo tized and an antidiazotate thereof, said compound containing a molecular grouping selected from the group consisting of mercapto-group, ethinylgroup and imino-group, the hydrogen atom of said molecular grouping being capable of being exchanged for a metal, into an image of the corresponding organic silver compound, transforming said image into an azo-dyestufi picture and removing the remaining silver halide.

3. A process of producing colored photographic pictures which comprises exposing to light a photographic material provided with at least one emulsion layer containing a light-sensitive silver halide, transforming the latent image into 'a silher halide image, converting said silver halide image by 6-amino-2-mercapto-benzthiazole into an image'of the corresponding organic silver. compound and transforming said image into an azo-dyestuif picture.

' so 4. A process of producing colored photographic pictures which comprises exposing to light a photographic material'provided with at least one emulsion layer containing a light-sensitive silver halide, transforming the latent image into a silver halide image, converting said silver 'halide image by 3-amino-4-methoxyphenyl-methylethinylcarbinol into an image of the corresponding organic silver compound and transforming said image into an azo-dyestufi picture.

5. A process of producing colored photographic pictures which comprises expo ng to light a photographic material provided'with at least one emulsion layer containing a light-sensitive silver halide with the pyrazolone produced by condensing a-hydrazino-stearic acid with acetoacetic ester, transforming the latent image into a silver halide image, converting saidsilver halide image by ortho-aminophenyl-phenyl-ethinylcarbinolantidiazotate into an image of the corresponding 0 organic silver compound and transforming said image into an azo-dyestufi :picture; I LOTHAR JAKOB.

BRUNO WENDT. 1 

